Structural and electrochemical properties of binuclear complexes containing 1,10-phenanthroline-5,6-diolate as a bridging ligand

Journal Article · Wed Jul 10 04:00:00 EDT 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00014a014· OSTI ID:5942305

Fox, G A; Bhattacharya, S; Pierpont, C G ^[1]

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1. Univ. of Colorado, Boulder (United States)

Bis(triphenylphosphine)(1,10-phenanthroline-5,6-dilato)platinum(II), (PPh{sub 3}){sub 2}Pt(O{prime},O-PhD), may be prepared by treating 1,10-phenanthroline-5, 6-dione with Pt(PPh{sub 3}){sub 4}. The oxygen-bound diolate form of the PhD ligand can coordinate to an additional metal through the nitrogen donor atoms forming a binuclear complex with the (PPh{sub 3}){sub 2}Pt(O{prime},O-PhD) unit serving as a bipyridine-like ligand. Complexes of general form (PPh{sub 3}){sub 2}Pt(O{prime},O-PhD-N,N{prime})ML{sub n} have been prepared with ML{sub n} = PdCl{sub 2}, Ru(PPh{sub 3}){sub 2}Cl{sub 2}, and Pt(DBCat). The Pt,Pd and Pt,Ru complexes could not be characterized from elemental analytical data due to the presence of nonstoichiometric solvate molecules; crystallographic structure determinations provided information on both complexes. Structural features of both molecules include similar, planar P{sub 2}Pt(PhD)MCl{sub 2} regions, with additional axial PPh{sub 3} ligands for M = Ru, and C-O lengths for the PhD ligand that are typical of catecholate ligands. The electrochemical properties of the complexes consist of first and second electron oxidations of the PhD bridge for all three species, with an additional Ru{sup II}/Ru{sup III} couple for (PPh{sub 3}){sub 2}Pt(O{prime}, O-PhD-N, N{prime})Ru(PPh{sub 3}){sub 2}Cl{sub 2} and two additional catecholate oxidations for the DBCat ligand of (PPh{sub 3}){sub 2}Pt(O{prime}, O-PhD-N, N{prime})Pt(DBCat). Similarities in bonding between L{sub n}M(O{prime},O-PhD) species and the bipyridine and 1, 10-phenanthroline ligands is described. 13 refs., 3 figs., 6 tabs.

• OSTI ID: 5942305
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Vol. 30:14; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

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AROMATICS
AZAARENES
CHEMISTRY
COMPLEXES
CRYSTAL STRUCTURE
DATA
ELECTROCHEMISTRY
EXPERIMENTAL DATA
HETEROCYCLIC COMPOUNDS
INFORMATION
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PALLADIUM COMPLEXES
PHENANTHROLINES
PLATINUM COMPLEXES
RUTHENIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES